JPH1072377A - Process for reaction of organic compounds and catalyst therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable the obtaining of a process by which a high yield or a quantitative conversion rate can be achieved by reacting an organic compound in the presence of a catalyst containing a specific metal supported on a specified support. SOLUTION: An organic compound is reacted in the presence of a catalyst comprising (B) ruthenium alone or together with at least one group Ib, IIb or VIIIb as an active metal in an amount of 0.01-30wt.%, based on the total weight of the catalyst applied to (A) a support in which 50-90% of the pore volume of the support comprises mesepores having a pore diameter within the range of 2-50nm and the sum of the pores volumes is 100%. The reaction is preferably hydrogenation, dehydrogenation, hydrogenolysis, etc., especially preferably the hydrogenation. The organic compound is low molecular weight monomers and polymeric organic compounds, etc., which can be catalytically reacted. Thereby, the reaction can be carried out at a high space velocity and an ultrahigh turnover number for a long on-stream time, and a high yield and a high purity of a hydrogenation product can be expected.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to organic compounds in the presence of ruthenium and optionally one or several other Group Ib, VIIb or VIIIb metals applied to a porous support in the presence of a catalyst. To a reaction.

In one embodiment, the invention relates to an aromatic compound having at least one hydroxyl group attached to the aromatic nucleus, preferably at least one hydroxyl group to the aromatic nucleus, the reaction of C ₁ -C ₁₀ alkyl group and / or at least one C ₁ -C10 aromatics alkoxy groups are bound optionally substituted in number, preferably relates to the hydrogenation process. further,
In the process according to the invention, preference is given to using monoalkyl-substituted phenols.

[0003]

BACKGROUND OF THE INVENTION Mononuclear or polynuclear aromatic compounds are preferably hydrogenated in the presence of the catalysts described herein to produce the corresponding cycloaliphatic compounds, the hydroxyl groups being retained during the process.

Cycloaliphatic alcohols, especially alkylcyclohexanols, are important intermediates in the manufacture of various perfumes, medicaments and other organic fine chemicals. The above cycloaliphatic alcohols are easily obtained by catalytic hydrogenation of the corresponding aromatic precursors.

[0005] Processes for the production of alkylcyclohexanols by catalytic hydrogenation of the corresponding alkylphenols are known. The hydrogenation of alkylphenols to form the corresponding alkylcyclohexanols in the presence of hydrogenation catalysts, especially those applied to supports, has been described in many places.

The catalysts used are metal rhodium, rhodium / platinum and rhodium / ruthenium alloys on a catalyst support, and ruthenium, palladium or nickel.
The catalyst supports used are carbon, barium carbonate and especially aluminum oxide.

[0007] Polish Patent (PL) 137526 describes the hydrogenation of p-tert-butylphenol to form p-tert-butylcyclohexanol using a nickel catalyst.

[0008] German Patent (DE-A) 340134
No. 3 and EP 0141544 describe a process for the preparation of 2- and 4-tert-butylcyclocyclohexanol from 2- and 4-tert-butylphenol by catalytic hydrogenation. The hydrogenation is carried out in two steps, in the first step a palladium catalyst on Al ₂ O ₃ support is used, in the second step Al
A ruthenium catalyst on a ₂ O ₃ support is used. The metal content on the carrier is between 0.1 and 5% by weight. The carrier is not special. The process is carried out with a recycle of the product under a pressure of 300 bar, preferably to obtain cis-tert-butylphenol, with 0.1-0.5% by-product during the process.
Is formed.

[0009] US Patent No. 2927127 describes:
A process for the preparation of p-tert-butylcyclohexanol and its esters by catalytic hydrogenation of p-tert-butylphenol is described. The catalyst used was 5% rhodium on carbon, 5% palladium on barium carbonate and 5% ruthenium on carbon. When using ruthenium on carbon, it was carried out under a pressure of 70-120 bar and at a temperature of 74-93 ° C. The hydrogenated product obtained contains 66% of the cis isomer.

[0010] German Patent (DE-A) 290966
No. 3 describes a process for preparing cis-alkylcyclohexanols by catalytic hydrogenation of the corresponding alkylphenols. The catalyst used was ruthenium on an Al ₂ O ₃ support. The method was performed under pressures of 40, 60 and 80 bar. The obtained product was mainly cis-alkylcyclohexanol, and the obtained by-product contained 0.1 to 1% of alkylbenzene.

In one embodiment, the present invention provides an aromatic compound having at least one amino group attached to an aromatic nucleus;
Preferably, the aromatic nucleus has at least one optionally substituted C ₁ -C in addition to the at least one amino group described above.
_It relates to a reaction, preferably a hydrogenation process, of an aromatic compound having a ₁₀ alkyl group and / or at least one C ₁ -C ₁₀ alkoxy group bonded thereto. In particular, monoalkyl-substituted amines are preferably used.

Mononuclear or polynuclear aromatic compounds are hydrogenated to the corresponding cycloaliphatic compounds in the presence of the catalysts described herein, the amino groups being retained during the process.

Cycloaliphatic amines, in particular optionally substituted cyclohexylamines and dicyclohexylamines, are useful for the preparation of anti-aging agents for elastic rubbers and plastics materials, as anticorrosives and as intermediates for plant protection agents and textile auxiliaries. Used as In addition, cycloaliphatic diamines are used in the production of polyamide and polyurethane resins and as curing agents for epoxy resins.

It is known that cycloaliphatic amines can be prepared by catalytic hydrogenation of the corresponding mono- or polynuclear aromatic amines. The preparation of the corresponding cycloaliphatic amines by hydrogenation of aromatic amines in the presence of hydrogenation catalysts, in particular of catalysts applied to supports, has been described in numerous places.

The catalyst used is, for example, Raney cobalt containing a basic additive (JP-B-43-3180), nickel catalyst (US Pat. No. 4,914,239, DE80)
No. 5518), a rhodium catalyst (BE739376, JP-B-45-19901, JP-B-47-35424).
Publication) and a palladium catalyst (US Pat. No. 3,520,928)
EP 501265, EP 53818, JP-B-59-
196843). However, catalysts containing ruthenium are often used.

German Patent DE 2 13 247 47 describes a process for the hydrogenation of mononuclear or polynuclear aromatic diamines which is carried out in the presence of a suspended ruthenium catalyst to produce the corresponding cycloaliphatic amines. ing.

EP-A-67058 describes a process for the preparation of cyclohexylamine by catalytic hydrogenation of the corresponding aromatic amine. The catalyst used is ruthenium metal in finely divided form on activated aluminum pellets. After four recycles, the catalyst begins to lose its activity.

EP-A-324987 discloses the hydrogenation of optionally substituted anilines using a ruthenium- and palladium-containing catalyst on a support, further containing an alkali metal compound exhibiting an alkaline reaction which acts as a modifier. To a mixture of optionally substituted cyclohexylamines and optionally substituted dicyclohexylamines. A radically similar process is described in EP 501265, in which the catalyst contains as modifier a niobate, a tantalum or a mixture of the two.

US Pat. No. 2,606,925 describes:
A process for the preparation of aminocyclohexyl compounds by hydrogenation of the corresponding aromatic compounds is described, wherein a ruthenium catalyst is used, the active catalyst component of which is elemental ruthenium,
Ruthenium oxide and ruthenium are selected from ruthenium salts which are present as anions or cations. As shown by the example of the method, the catalyst is prepared in a separate step, dried and introduced into the reaction vessel after a relatively long drying time.

Another process for the preparation of cyclohexylamine is described in US Pat. No. 2,822,392, the main feature of which is that the aniline and hydrogen used as starting materials react countercurrently with one another. Involves the use of special reactors.

US Pat. No. 3,636,108 and US Pat. No. 3,697,449 disclose the catalytic hydrogenation of nitrogen-containing aromatic compounds using a ruthenium catalyst which additionally contains an alkali metal compound as a modifier. About.

Common to all of the above processes is the use of a mesoporous support, typically having a surface area (BET) of between 50 m ² / g and 1000 m ² / g or more, to achieve high activity of the catalyst. is there.

In addition, apart from the high cost of the catalyst, especially during hydrogenations using rhodium-containing catalysts, relatively large amounts of alkylbenzenes and other unidentified compounds which form as decomposition products or by-products during the hydrogenation Has been found to be disadvantageous in that it frequently appears during such reactions. These by-products suppress the work-up and purification of the reaction products, especially when alkylcyclohexanols are to be used, for example, as perfumes or for perfume production. Furthermore, many of the catalysts used in the above processes are rapidly deactivated, especially when the hydrogenation is carried out at relatively high temperatures to promote the reaction rate.

The present invention provides, in another embodiment, the reaction, preferably hydrogenation, of a polymer having groups to be reacted, preferably having nitrile groups, by using a ruthenium-containing catalyst as described herein. About the method.

The process for hydrogenating polymers having at least one unit to be hydrogenated is known per se. One class of polymers that has been used particularly intensively in the past as starting materials in processes for hydrogenating polymers are those that contain nitrile groups. In the process according to the invention, these polymers are also preferably used to obtain the corresponding polymers containing amino groups.

The polymers having amino groups as obtained by this method can be used, for example, as branching agents, cross-linking agents or complexing agents, of which the preferred applications are papermaking, detergent industry, adhesives And cosmetics.

In the past, several systems have been described for reducing polymers having nitrile groups in order to obtain polymers having amino groups. Of these, for example, German Patent (DE) 1226303
In addition to the reduction using complex metal hydrides as described in No. 2 and No. 2,905,671, hydrogenation with hydrogen must also be mentioned.

Hydrogenation with hydrogen is significantly less expensive and-unlike reduction with complex metal hydrides-requires only catalytic amounts of metal-containing components, which has economic and ecological advantages. Have.

In the past, hydrogenation with hydrogen has been carried out using homogeneous or heterogeneous catalysts.

While homogeneous catalysts are chemically elegant, the separation of the catalyst is significantly more complex than a heterogeneous catalyst. The use of homogeneous catalysts is particularly disadvantageous in catalytic processes using polymers, since the separation of the polymer product from the catalyst by distillation is not possible. If the polymer product is to be separated from the homogeneous catalyst by crystallization or precipitation, repetitive crystallization is necessary, as inclusions of the catalyst result in prolonged time and increased costs.

The problems attributed to catalyst separation do not occur in heterogeneous catalytic reactions. However, known heterogeneous catalysis methods for polymers containing nitrile groups, such as those performed by using a Raney metal fixed bed catalyst, include:
Often, only poor yields and selectivities result.

US Pat. No. 2,456,428 describes:
It describes the hydrogenation of poly (acrylonitrile), poly (methacrylonitrile) and similar polymers. After hydrogenation in the presence of Raney nickel as a catalyst, the unreacted polymer must be separated off before further processing. Certainly, the reactions described here do not proceed quantitatively and the yields achieved by the method are inadequate.

According to US Pat. No. 3,122,526 for hydrogenating cyanoethylated poly (acrylonitrile) by using Raney nickel as catalyst, low yields of less than 10% of the corresponding amines are obtained. U.S. Pat. No. 2,585,583 describes the hydrogenation of butadiene and acrylonitrile and methacryloyl tolyl copolymers by using a suspension hydrogenation catalyst, respectively. United States Patent (US) No. 2
647146 describes the hydrogenation of butadiene oligomers having nitrile end groups by using a mixture of two suspension catalysts (Pd on carbon and Ni on diatomaceous earth). According to these two methods, the catalyst used in each case must be separated from the reaction solution by filtration.

To summarize the above, the hydrogenation of polymers having nitrile groups to obtain polymers having amino groups is known per se, but good yields of polymers having amino groups have been up to now. It was only obtained by using a turbid catalyst. However, these catalysts must be separated from the reaction solution by filtration and cannot be used in fixed bed reactors.

In another embodiment, the present invention relates to the formation of C on a porous support in the presence of ruthenium or palladium as active metal and optionally one or several other Group Ib, VIIb or VIIIb metals. -C
The present invention relates to a method for hydrogenating a polymer having multiple bonds.

Polybutadiene, poly (styrene-co-
Butadiene), poly (styrene-co-isoprene),
Polymers having CC multiple bonds, such as poly (acrylonitrile-co-butadiene) and the like, are of great industrial importance, especially for applications involving food packaging, impact resistant materials, adhesives and the like. The region of unsaturation renders these polymers susceptible to thermal and oxidative degradation, so that these polymers usually exhibit poor atmospheric decomposition resistance. C-
Polymers in which the CC multiple bond, such as the C double bond, has been hydrogenated usually show a pronounced stability improvement.

In the past, a number of homogeneous and heterogeneous catalysts have been described for this hydrogenation.

For example, US Pat. No. 3,595,529
No. 5,359,942, No. 3,700,633 and No. 3,810,957, which involve a hydrogenation using a homogeneous catalyst, show a high degree of selectivity for the hydrogenation of unsaturated CC bonds. That is, the aromatic regions present in the polymer remain substantially unhydrogenated. However, such a process can only separate the catalyst used in dissolved form from the desired product only by using complex processing steps which undesirably increase the cost of the process.

If the hydrogenation is carried out using a heterogeneous catalyst, there is no problem of catalyst separation. Exhibiting significantly lower selectivity than hydrogenation carried out using such a catalyst system as described, for example, in US Pat. No. 3,333,024 and Belgian patent application 873348,
That is, the aromatic regions present in the polymer are also hydrogenated to a significant extent.

For this reason, in the past, heterogeneous catalysts capable of selectively hydrogenating ethylenic double bonds in polymers have been sought.

British Patent (GB-A) 2061961 describes a suspension catalyst consisting of 5% of rhodium on activated carbon, this catalyst being a triblock poly (styrene-co-butadiene) with a molecular weight of only up to 60000. Can only be used for the hydrogenation of

US Pat. No. 4,560,817 describes:
Poly (styrene-c using catalysts partially poisoned by alkali metal or alkaline earth metal alkoxides
describes the selective hydrogenation of (o-butadiene), in which the polymer is reacted during hydrogenation with a mixture of hydrogen and ammonia or an organic amine. To achieve sufficient activity, the hydrogenation temperature is close to the decomposition temperature of the polymer.

Catalysts consisting of macroporous support materials to which Group VIIIB metals have been applied and which can be used for the hydrogenation of carbon-carbon double bonds are described in US Pat.
S) No. 5110779. 90% of the pores present in the support material of the catalyst described in this specification
Has a diameter greater than 100 nm. The ratio of the surface area of the metal to the surface area of the support is between 0.07 and 0.75: 1. The patent specifically emphasizes the high surface area of the metal compared to the surface area of the support, which is stated to be surprising as such catalysts still have a high activity.

Furthermore, the present invention provides a method for producing at least one C = O
Organic compounds having a group, such as ketones, aldehydes,
The present invention relates to a method for reacting, preferably hydrogenating, a carboxylic acid or a derivative thereof or a mixture of two or more thereof.

[0045]

SUMMARY OF THE INVENTION Thus, one aspect of the present invention is as follows.
One objective is to react organic compounds as defined above, where very high yields or almost quantitative conversions are achieved,
It is preferable to provide a hydrogenation method.

Another object of the present invention is to provide such a process in which only a minimum content of by-products or decomposition products is produced during the hydrogenation.

The process can be carried out at high space velocities and very high turnover numbers with a long on-stream time, the corresponding hydrogenated products having high yields and purity. Should be obtained at

[0048]

SUMMARY OF THE INVENTION One or many of the above objects are attained by using ruthenium alone or at least one Ib, VIIb or V as an active metal supported on a carrier.
Together with the group IIIb metal, 0.0
The reaction of organic compounds in the presence of a catalyst comprised in an amount of 1 to 30% by weight, preferably achieved by a hydrogenation process, wherein 10 to 50% of the pore volume of the support is 50 nm to 10000 nm
And 50 to 90% of the pore volume of the carrier consists of mesopores having a pore size in the range of 2 to 50 nm, and the sum of the pore volumes is 100%. is there.

In another embodiment, the present invention provides that the active metal applied to the support is ruthenium alone or at least one of Ib, VIIb or VIIIb.
Together with the group metal, from 0.01 to 30 based on the total weight of the catalyst.
Palladium as active metal, alone or together with at least one Group Ib, VII or VIIIb metal, in the presence of a catalyst which is contained in an amount of% by weight or applied to the support,
For the reaction of a polymer having C—C multiple bonds, preferably in a hydrogenation process, in the presence of a catalyst which is present in an amount of 0.01 to 30% by weight relative to the total weight of the catalyst, the catalysts each have a pore in the support. 10 to 50% of the volume is 50 nm to 10
It consists of macropores having a pore size in the range of 000 nmno, and 50-90% of the pore volume of the carrier consists of mesopores having a pore size in the range of 2-50 nm, and the sum of the pore volumes is There is a feature.

The above and other objects of the invention are achieved by a reaction as described in the dependent claims, preferably by a hydrogenation process. One particular advantage of the process according to the invention is that very good results are achieved when only small metal contents in the catalyst are used.

Furthermore, the process according to the invention shows a high number of revolutions at high space velocities over long catalytic times. The space velocity is the space-time yield of the process, ie the starting material (e) reacted per unit time per unit weight of catalyst present.
duct). The working time is the time over which the weight of the starting material which can be brought into contact with the catalyst without reacting to the properties of the starting material and without significantly modifying the properties of the product is reacted.

The present invention furthermore relates to a catalyst as defined herein, namely ruthenium, as active metal applied to a support, in an amount of 0.01 to 30% by weight, based on the total weight of the catalyst, alone or with ruthenium. At least one Ib, VIIb or V
As an active metal applied to a catalyst or a support containing a group IIIb metal, as active metal, 0.00% of the total weight of the catalyst
For catalysts containing palladium, alone or together with at least one Group Ib, VIIb or VIIIb metal, in an amount of 1 to 30% by weight, the catalysts each have between 10 and 50% of the pore volume of the support between 50 nm and 10000 nm. Macropores having a pore size in the range of 5% of the pore volume of the support.
0 to 90% include mesopores having a pore size in the range of 2 to 50 nm, wherein the sum of the pores is 100%.

Compounds The term "organic compound" as used within the present invention is intended to include all organic compounds, including low molecular weight (monomer) and polymeric organic compounds, which can be catalytically reacted, especially C--C2 Includes compounds having a group that can be treated with hydrogen, such as a heavy bond or a CC triple bond. The term includes low molecular weight organic compounds as well as polymers. "Low molecular weight organic compounds" are compounds having a molecular weight of 500 or less. The term "polymer" is defined with respect to molecules having a molecular weight greater than about 500.

The invention relates in particular to a process for reacting an organic compound in the presence of a catalyst as defined herein, wherein the reaction comprises hydrogenation, dehydrogenation, hydrocracking, aminating hydrogenatio.
n) or dehalogenation, more preferably hydrogenation.

In particular, organic compounds having one or several of the following structural units can be used:

[0056]

Embedded image

The method of the present invention comprises an aromatic compound having at least one hydroxyl group bonded to an aromatic ring, an aromatic compound having at least one amino group bonded to an aromatic ring, a ketone, an aldehyde and a carboxylic acid. Acids or derivatives thereof,
The group consisting of polymers having at least one CC double bond, polymers having at least one C１O group, polymers having at least one C≡N group, and mixtures of two or more thereof It is particularly suitable for reacting, preferably hydrogenating, an organic compound selected from:

In the process according to the invention, organic compounds having units of different structure as defined above, for example organic compounds having a CC multiple bond and a carbonyl group, can be reacted, since the invention The catalyst used in the process of (1) can selectively hydrogenate one of the two groups initially, ie, achieve about 90-100% hydrogenation of these groups, while the other Because it is initially reacted to the extent of less than 25%, generally from 0 to about 7%, preferably hydrogenated. In general, first the CC multiple bond and then the C = O group, respectively, are reacted, for example hydrogenated.

The term "aromatic compound having at least one hydroxyl group attached to an aromatic ring" or "aromatic compound having at least one amino group attached to an aromatic ring"
Is a unit of the structure (I):

[0060]

Embedded image

All compounds having [where R is a hydroxyl group or an amino group] are meant.

In the method of the present invention, at least one hydroxyl group and at least one unsubstituted or substituted C ₁ -C ₁₀ alkyl group and / or C ₁ -C ₁₀ alkoxy group are bonded to the aromatic ring. When aromatic compounds are used, the resulting isomer ratio of cis to trans products can be varied within wide ranges depending on the reaction conditions (temperature, solvent). Furthermore, the resulting compounds can be processed further without further purification steps, since the formation of alkylbenzene is virtually completely avoided.

Aromatic compounds having at least one amino group bonded to an aromatic ring, such as the compounds having at least one hydroxyl group bonded to an aromatic ring, are also hydrogenated by the method of the present invention. The corresponding alicyclic compounds can be obtained with high selectivity. For amines which are additionally substituted by C ₁ -C ₁₀ alkyl groups and / or C ₁ -C ₁₀ alkoxy groups, the statements made above regarding the ratio of cis and trans isomers apply.

In particular, this embodiment substantially completely avoids the formation of deaminated products such as cyclohexane or partially hydrogenated dimerized products such as phenylcyclohexylamine.

Specifically, the following compounds are used in the method of the present invention.
Can be reacted using:At least one hydroxyl group attached to the aromatic ring
Aromatic compounds  At least one hydroxyl group and preferably at least
And one unsubstituted or substituted C₁~ C_TenAlkyl group and / or
Or an aromatic compound having an alkoxy group bonded to an aromatic ring
Is reacted, preferably hydrogenated, according to the method of the invention,
The corresponding alicyclic compounds can be obtained, these compounds
It is also possible to use mixtures of two or several of the above.
The aromatic compound used is a monocyclic or polycyclic aromatic compound.
It may be. Aromatic compounds have few attached to the aromatic ring
Contains at least one hydroxyl group; the simplest of this group
A simple compound is phenol. Aromatic compounds are preferred
Or one hydroxyl group per aromatic ring,
One or several aromatic rings may comprise one or several alkyl and / or
Is an alkoxy group, preferably C₁~ C_TenAlkyl and / or
Or an alkoxy group, particularly preferably C₁~ C_TenArchi
Groups, especially methyl, ethyl, propyl, isopropyl
Butyl, isobutyl and tert-butyl groups
Optionally substituted; C of the alkoxy groups₁~ C₈A
Alkoxy groups such as methoxy, ethoxy, propoxy
Si, isopropoxy, butoxy, isobutoxy and te
An rt-butoxy group is preferred. One or several aromatic rings
And alkyl and alkoxy groups are unsubstituted or substituted.
Logen atoms, especially fluorine atoms, or other suitable inert radicals
It may be substituted by a substituent.

Preferably, at least one compound which can be reacted, preferably hydrogenated, according to the invention is
It preferably has 1 to 4, in particular 1 C _{1 to} C ₁₀ alkyl group, the alkyl group preferably being located on the same aromatic ring as one or several hydroxyl groups. Preferred compounds are those in which the alkyl group is o
A (mono) alkylphenol which may be in the n, m or p position. Trans-alkylphenols, also known as 4-alkylphenols, are particularly preferred, wherein the alkyl group preferably has 1 to 10 carbon atoms and is especially a tert-butyl group. 4-tert-
Butylphenol is preferred. Polycyclic aromatic compounds which can be used according to the invention are, for example, β-naphthol and α-naphthol.

The aromatic compound in which at least one hydroxyl group and preferably at least one unsubstituted or substituted C ₁ -C ₁₀ alkyl group and / or alkoxy group are bonded to one aromatic ring is an alkylene group , Preferably a plurality of aromatic rings linked via a methylene group. Alkylene group which forms a bond, preferably a methylene group may have one or several alkyl substituents, alkyl substituents may be C ₁ -C ₂₀ alkyl group, preferably a C ₁ ~ C ₁₀ alkyl group, particularly preferably methyl, ethyl, propyl, isopropyl, butyl or tert- butyl.

Each of the aromatic rings in these compounds is
It can have at least one attached hydroxyl group. Examples of such compounds include an alkylene group at the 4-position,
Preferred is bisphenol linked via a methylene group.

In the process according to the invention, it is particularly advantageous to react phenol substituted by C ₁ -C ₁₀ alkyl groups, preferably C ₁ -C ₆ alkyl groups, or a mixture of two or several of these compounds. Preferably, an alkyl group may be unsubstituted or substituted by an aromatic group.

In another preferred embodiment of the method, p-tert-butylphenol, bis (p-hydroxyphenyl) dimethylmethane or a mixture thereof is reacted.

At least one amino group is bonded to an aromatic ring
The method of the present invention can react, preferably hydrogenate, an aromatic compound in which at least one amino group is attached to an aromatic ring to obtain the corresponding cycloaliphatic compound, Mixtures of two or several of these compounds can also be used.
The aromatic compound may be a monocyclic or polycyclic aromatic compound. The aromatic compound has at least one aromatic compound attached to the aromatic ring.
Contains two amino groups. The aromatic compound is preferably an aromatic amine or diamine, and one or several aromatic rings or amino groups are one or several alkyl and / or alkoxy groups, preferably C ₁ -C ₂₀ alkyl groups, especially It may be substituted by methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl groups. Among the alkoxy groups, C ₁ -C ₈ alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy and tert-butoxy groups are preferred. One or several aromatic rings and alkyl and alkoxy groups may be unsubstituted or substituted by halogen atoms, especially fluorine atoms or other suitable inert substituents.

The aromatic compound in which at least one amino group is bonded to an aromatic ring may have a plurality of aromatic rings bonded through an alkylene group, preferably a methylene group. Alkylene group which forms a bond, preferably a methylene group may have an alkyl substituent, the substituent may be a C ₁ -C ₂₀ alkyl group, preferably a C ₁ -C ₁₀ alkyl group, in particular Preferably it is methyl, ethyl, propyl, isopropyl, butyl, sec-butyl or tert-butyl.

The amino group bonded to the aromatic ring may be unsubstituted or substituted by one or two of the above-mentioned alkyl groups.

Particularly preferred compounds are aniline, naphthylamine, diaminobenzene, diaminotoluene and bis-p-aminophenylmethane or mixtures thereof.

Compounds Having a C ＝ O Group Within the process of the invention, compounds having a C ＝ O group, ie especially aldehydes, ketones, carboxylic acids and derivatives thereof, such as carboxylic esters, carboxylic halides and carboxylic anhydrides It is also possible to react a product and a mixture of two or several of the abovementioned compounds.

Aldehydes and ketones, preferably those having 1 to 20 C atoms, such as formaldehyde, acetaldehyde, propionaldehyde, n
-Butyraldehyde, valeraldehyde, caproaldehyde, heptaldehyde, phenylacetaldehyde,
Acrolein, crotonaldehyde, benzaldehyde, o-, m-, p-tolualdehyde, salicylaldehyde, anisaldehyde, vanillin, cinnamaldehyde, acetone, methyl ethyl ketone, 2-pentanone,
3-pentanone, 2-hexanone, 3-hexanone, cyclohexanone, isophorone, methyl isobutyl ketone, mesityl oxide, acetophenone, propiophenone, benzophenone, benzalacetone, dibenzalacetone, benzalacetophenone, glycolaldehyde, glyoxal, , 3-butanedione, 2,4-
Pentanedione, 2,5-hexanedione, terephthalaldehyde, glutaraldehyde, diethyl ketone, methyl vinyl ketone, acetylacetone, 2-ethylhexanal, or a mixture of two or more of these can be used.

In addition, polyketones such as copolymers of ethylene and CO are also used.

Furthermore, carboxylic acids and their derivatives, preferably those having 1 to 20 C atoms, can be reacted. In particular, there may be mentioned: carboxylic acids, such as formic acid, acetic acid, propanoic acid, butanoic acid, isobutanoic acid, n-valeric acid, pivalic acid, caproic acid, heptanoic acid, octanoic acid, decanoic acid, lauric acid, myristic. Acid, palmitic acid, stearic acid, acrylic acid, methacrylic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, benzoic acid, phenylacetic acid, o-, m-, p-toluic acid,
o-, p-chlorobenzoic acid, o-, p-nitrobenzoic acid, salicylic acid, p-hydroxybenzoic acid, anthranilic acid, p-aminobenzoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, Pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, and mixtures of two or more thereof.

Carboxylic acid halides, for example chlorides and bromides of the abovementioned carboxylic acids, in particular acetyl chloride or acetyl bromide, stearic acid chloride or -bromide and benzoic acid chloride or -bromide, which are dehalogenated .

Carboxylic esters, for example the abovementioned C ₁ -C ₁₀ alkyl esters of carboxylic acids, especially methyl formate, acetate, butyl butanoate, dimethyl terephthalate, dimethyl adipate, methyl (meth) acrylate, butyrolactone, Caprolactone, and polycarboxylates, such as polyacrylates and polymethacrylates, and copolymers and polyesters thereof, such as poly (methyl (meth) acrylate); these esters are especially hydrogenated;
That is, the ester reacts to produce the corresponding acid and alcohol.

Carboxylic anhydrides, such as the carboxylic anhydrides mentioned above, in particular acetic anhydride, propionic anhydride,
Benzoic anhydride and maleic anhydride. Carboxamide,
For example, the amides of the carboxylic acids mentioned above, such as formamide, acetamido, propionamide, stearoamide and terephthalamide.

In addition, hydroxycarboxylic acids such as butyric, malic, tartaric or citric acid, or amino acids such as glycerin, alanine, proline and arginine can also be reacted.

Nitriles Further nitriles, preferably aliphatic or aromatic mono- or di-nitrile, such as acetonitrile, propionitrile, butyronitrile, nitrile stearate, nitrile isocrotonic acid, 3-butynenitrile, 2,3-butadienenitrile, , 4-pentadienenitrile, 3
-Hexene-1,6-dinitrile, chloroacetonitrile, trichloroacetonitrile, nitrile butyrate, phenolacetonitrile, 2-chlorobenzonitrile, 2,
6-dichlorobenzonitrile, isophthalonitrile, especially aliphatic α, ω-dinitrile, such as succinonitrile, glutaronitrile, adiponitrile, pimelinonitrile, and suberonitrile or aminonitrile, such as 4-aminobutanoitrile, -Nitrile aminopentanoate, nitrile 6-aminohexanoate, nitrile 7-aminoheptanoate and nitrile 8-aminooctanoate.

In addition, the following reactions can be carried out within the process according to the invention: hydrogenation of aromatic compounds, such as benzene, toluene, xylene, naphthalene and substituted derivatives thereof, to the corresponding cycloaliphatic compounds; Alkenes or alkynes such as ethylene, propylene, 1-, 2-
Hydrogenation of butenes, 1-, 2-, 3- and 4-octene, butadiene and hexatriene to the corresponding alkanes; nitroalkanes such as nitroethane, nitromethane, nitropropane and 1,1-dinitroethane
Hydrogenation to the corresponding amines; hydrogenation of imines such as quinone imines, ketimines, ketenimines or aliphatic imines such as propioimine, hexanimine; organic compounds containing halogen atoms, especially aromatic halogen containing compounds such as chlorobenzene and bromobenzene ,
Dehalogenation of organic compounds including bromotoluene and chlorotoluene, and chloroxylol and bromoxylol, compounds having one or more substituted halogen atoms;
That is, aminating hydrogenati of an alcohol such as vinyl alcohol.
on) can be used.

Furthermore, secondary amines can be prepared within the process of the invention by reacting the oxime or starting from ketones and primary amines.

Polymers The catalysts according to the invention can be used for the hydrogenation, dehydrogenation, hydrocracking, amination hydrogenation and dehalogenation of large molecules, preferably polymers.

Accordingly, the present invention relates to a process for reacting a polymer containing at least one catalysable group in the presence of a catalyst as identified above, and to a method for reacting a polymer such as a polyester of a dicarboxylic acid in the presence of the catalyst described above. =
Hydrogenation of polymers containing O groups, unsaturated monocarboxylic acids such as poly (meth) acrylates, olefin / CO-copolymers or polyketones, and nitrile groups such as styrene and butadiene copolymers and acrylonitrile copolymers. Preference is given to the hydrogenation of the resulting polymers and the amination of the polyvinyl alcohols and polyketones.

In particular, the present invention provides at least one C = O
The invention relates to a process for hydrogenating polymers containing groups or polymers containing at least one C≡N group.

The term “polymer containing at least one catalysable group” refers to all polymers containing such groups, in particular units having the structure (I) to (VIII) as defined above for monomeric compounds. Or a polymer containing a halogen atom. It goes without saying that the polymers mentioned contain at least one respective unit and also that one or more of the units having two or more of the structures can be present in the polymer reacted according to the invention.

The average molecular weight of the polymer to be reacted within the process of the present invention generally ranges from about 500 to about 500,000, preferably from about 1000 to about 100,000, more preferably about 1 to about 100,000.
000 to about 50,000. However, it is also possible to react polymers having a higher molecular weight of up to one or several millions. When reacting polymers containing at least one C-C multiple bond, i.e. polymers containing repeating units of structures (I) and (II) as defined above, these polymers are generally from about 5,000 to about 10,000
00, preferably from about 50,000 to 500,000, more preferably from about 150,000 to about 500,000.

It is preferable to use a polymer containing an olefinic double bond, and it is more preferable to use a polymer containing a diene unit and a copolymer containing a vinyl aromatic unit and a diene unit. In this reaction, in addition to the catalyst containing ruthenium as the active metal, a catalyst containing palladium as the active metal can also be used, and for the other reactions described here, ruthenium is preferably used as the active metal. Included catalysts are used.
In this regard, in addition to Ru and Pd, I as defined herein
It must be recognized that Group b, VIIb or VIIIb metals (of course different from Ru and Pd, respectively) can also be used.

Commonly used units include the usual polyunsaturated monomers containing from 3 to 12 carbon atoms,
Butadiene is preferred.

The copolymer to be hydrogenated may contain repeating units in a random, block or tapered distribution.

Aromatic monomers that may be present in the polymer to be hydrogenated in the process of the present invention include monovinyl-substituted and polyvinyl-substituted aromatic compounds, with the preferred monomers being styrene, α-methylstyrene, acrylonitrile, methacryloyl tolyl and Divinylbenzene.
In addition, mixtures of vinyl aromatic monomers and / or diolefin monomers can be present in the polymer to be hydrogenated, optionally together with conventional olefin monomers.

Examples of polymers to be reacted, preferably hydrogenated, in the process according to the invention include: C
A polymer having a -C double bond, such as poly (2,3
Polybutadiene, polyisoprene, polyacetylene and polycyclopenta- and -hexadiene; polymers having a CC triple bond, such as polydiacetylene; terpolymers of polystyrene, acrylonitrile, butadiene and styrene, and styrene and Polymers having aromatic groups, such as copolymers of acrylonitrile; copolymers of polyacrylonitrile, polyacrylonitrile with comonomers such as, for example, vinyl chloride, vinylidene chloride, vinyl acetate or ((meth) acrylates or mixtures of two or more thereof) A polymer having a CO double bond such as polyester, polyacrylamide, poly (acrylic acid), polyurea and polyketone; like polysulfone and polyethersulfone Polymers having C-S double bond;
Halogen-containing polymers such as poly (vinyl chloride) and poly (vinylidene chloride); and nitro-containing polymers obtainable, for example, by nitration of polyolefins by a polymer-analogous reaction.

Examples of polymers advantageously used within the present invention are polyisoprene, polybutadiene, ethylene / CO
Copolymers, propylene / CO copolymers, poly (methyl (meth) acrylate), polyterephthalate, polyadipate, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-styrene copolymer, styrene-isoprene-styrene-triblock Copolymers, styrene-butadiene-styrene-triblock copolymers and styrene-butadiene-styrene-star block copolymers.

In general, a complete reaction of the starting materials introduced is achieved. However, the reaction, preferably the hydrogenation, can be effected, for example, by appropriate choice of the temperature, for example the H ₂ pressure and the amount of H ₂ , for example, by reacting only one of the groups to be hydrogenated, for example the group to be hydrogenated. Other species can also be implemented so that they are not hydrogenated.

The process of the present invention comprises reacting, preferably, a polymer comprising units of different structure as defined above, for example a polymer comprising CC multiple bonds and C ＝ O and / or C≡N groups. Are suitable for hydrogenation, since the catalysts of the present invention initially react selectively with C--C multiple bonds, for example to achieve about 90-100% hydrogenation of these groups. At the same time, C ＝ O groups and / or C≡N groups are reacted, for example hydrogenated, up to 25%, generally of the order of 0 to about 7%.

Further, the catalyst used in the process of the present invention can achieve hydrogenation of C—C multiple bonds, for example up to about 90 to 100% of the ethylenically unsaturated region, and an aromatic region of 25%. The method of the present invention is particularly suitable for hydrogenating high molecular weight polymers containing both CC multiple bonds and aromatic groups, since they are generally hydrogenated to below 0-7%.

After the end of this reaction, preferably hydrogenation of the C—C multiple bond, other unsaturated groups present in the polymer, for example the C 反 応 O group, are reacted almost quantitatively by introducing further hydrogen. Preferably hydrogenation is of course possible.

The method according to the invention can be used on living polymers which have already been isolated.

Catalysts The catalyst to be used in the process according to the invention comprises, on a suitable support, ruthenium or palladium and optionally at least one catalyst.
It can be produced on an industrial scale by applying species Ib, VIIb or VIIIb metals. Application is
This can be done by impregnating the support material with an aqueous metal salt solution, such as a solution of a ruthenium or palladium salt, by spraying the support with a suitable metal salt solution or by any other suitable method. Suitable ruthenium or palladium salts for preparing ruthenium and palladium salt solutions and suitable salts of the Ib, VIIb and VIIIb metals are nitrates, nitrosyl nitrates, halides, carbonates, carboxylate, acetylacetone of the metals. Acid salts, chlorine complexes, nitrite complexes or amine complexes, with nitrates and nitrosyl nitrates being preferred.

In the case of a catalyst containing other metals in addition to ruthenium or palladium, a metal salt or a metal salt solution can be applied simultaneously or sequentially.

Next, the carrier coated or impregnated with a solution of a ruthenium salt, a palladium salt or a metal salt is dried, and the preferred temperature is 100 ° C. to 150 ° C. If desired, these carriers may be at 200 ° C to 600 ° C, preferably at 350 ° C.
It can be calcined at temperatures ranging from ~ 450 ° C. The coated carrier is then activated by treatment in a gas stream containing free hydrogen at a temperature ranging from 30C to 600C, preferably from 150C to 450C. Gas stream is preferably, H ₂ 50 to 100 volume% and N ₂ 0 to 50
% By volume.

If one or several Group Ib, VIIb or VIIIb metals in addition to ruthenium or palladium are to be applied to the support and if the application is to be carried out sequentially, the support is dried and, if necessary, It can be calcined in between, the drying temperature is from 100C to 150C and the calcination temperature is from 200C to 600C. The order in which the metal salt solutions are applied is arbitrary.

If one or several Group Ib, VIIb or VIIIb metals are to be applied to the support in addition to ruthenium or palladium, preference is given to using platinum, copper, rhenium, cobalt, nickel or mixtures thereof.

The solution of the ruthenium salt, palladium salt or metal salt is added to the support with an active metal, ruthenium or palladium applied to the support and optionally one or several Ib, V
The content of the group IIb or VIIIb metal is from 0.01 to 30% by weight, preferably from 0.01 to 30% by weight, based on the total weight of the catalyst.
It is applied in a proportion such that it is 10% by weight and more preferably 0.01 to 5% by weight.

The total metal surface area on the catalyst is preferably from 0.01 to 10 m ² / g of the catalyst, more preferably from 0.05 to 10 m ² / g.
5 m ² / g, most preferably 0.05~3m ² / g. The metal surface area is described in J. Lemaitre et al. "Char
actuation of Heterogen
eous Catalysts ", Ed. Franci
s Delannay, Marcel Dekker,
It was measured by a chemisorption method as described in New York (1984), pp. 300-324.

The ratio of the surface area of the at least one active metal to the surface area of the catalyst support in the catalyst used in the process of the present invention is less than about 0.3: 1, preferably less than about 0.1: 1, more preferably Is about 0.05: 1 or less, with a lower limit of about 0.0005: 1.

[0110] The carrier material used for the preparation of the catalyst to be used in the process of the carrier present invention has macropores and mesopores. Pure Applied Chem. 45, 71
The term "macropore" refers to pores having a diameter greater than 50 nm, and the term "mesopore" refers to about 2.
For pores having a diameter between 0 nm and about 50 nm.

The carrier used in the present invention had the following pore distribution formed: about 10 to about 50%, preferably about 15 to about 50%, more preferably 15 to about 50% of the pore volume. 45%, most preferably 30-40% is about 50n
consisting of macropores having a pore size from m to about 10,000 nm, from about 50 to about 90%, preferably from 50 to about 85%, more preferably from 55 to about 85%, most preferably from 60 to about 70% of the pore volume. Consists of mesopores having a pore size of 2 to about 50 nm, the sum of the pore volumes being 100%.

[0112] Preferably, about 500 meters ² / g of surface area of the support carrier material, more preferably from about 200~350m ² /
g, most preferably from about 200 to about 250m ² / g.

The surface area of the carrier is determined by the BET method with N ₂ absorption as specified in DIN 66131. The determination of the average pore size and the pore size distribution is in particular DIN6
Mercury intrusion method (Hg p.
osymmetry).

In general, all known catalyst support materials can be used, provided that the material has the pore size distribution defined above, but is not limited to activated carbon, silicon carbide, aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide, Preference is given to using magnesium, zinc oxide or mixtures thereof, more preferably aluminum oxide and zirconium dioxide.

The catalyst used in the present invention has a high conversion, (high turnover index),
Shows selectivity and long duration of action. When the catalyst proposed in the present invention is used for hydrogenation applications, subsequent purification is unnecessary since the hydrogenation products are obtained in high yield and purity. The conversion is substantially quantitative. The hydrogenated product thus obtained, in a preferred embodiment of the invention, can be used directly in the next processing step and does not have to be purified.

In the hydrogenation of aromatic compounds in which at least one hydroxyl group is attached to an aromatic ring, in particular in the hydrogenation of 4-alkyl or 4-alkoxy-substituted phenols as described above, mainly trans An alicyclic compound of the configuration is obtained. According to one embodiment of the invention, the content of the trans-configuration compound is at least 60%, preferably at least 65%. The conversion is quantitative in nature,
The content of residual aromatic compounds, based on the total production, is preferably not more than 0.01% by weight. According to a preferred embodiment of the present invention, the resulting hydrogenated product can be introduced directly into the next processing step and does not have to be purified.

Solvent or Diluent The reaction, preferably hydrogenation, in the process of the invention can be carried out in the absence of a solvent or diluent, ie it is not necessary that the reaction be carried out in solution.

It is also possible to react the polymer directly in the melt.

However, preference is given to using solvents or diluents. The solvent or diluent used may be a suitable solvent or diluent. The choice is not critical. For example, the solvent or diluent may contain a small amount of water if desired.

Examples of suitable solvents or diluents in the reaction, preferably hydrogenation, of an aromatic compound in which at least one hydroxyl group is bound to an aromatic nucleus include: such as tetrahydrofuran or dioxane Linear or cyclic ethers and alkyl groups are preferably from 1 to 10
Aliphatic alcohols having 3 carbon atoms, more preferably 3 to 6 carbon atoms.

Examples of preferably used alcohols are isopropanol, n-butanol, isobutanol and n-hexanol. Mixtures of these or other solvents or diluents can also be used.

Examples of suitable solvents or diluents in the reaction of aromatic compounds, in which at least one amino group is bound to an aromatic nucleus, preferably in hydrogenation, include: tetrahydrofuran or dioxane Linear or cyclic ethers and mono- or dialkylamines in which the ammonia and the alkyl group preferably have 1 to 3 carbon atoms, such as methylamine, ethylamine or propylamine, or the corresponding dialkylamine.

Mixtures of these or other solvents or diluents can also be used.

The amount of the solvent or diluent used in both of the above embodiments is not particularly limited and can be freely selected as required, but the concentration of the compound to be hydrogenated is preferably 10 to 70%. An amount that results in a weight percent solution is preferred.

When carrying out the process according to the invention, it is particularly preferred to use the product which forms during the reaction of the process, preferably hydrogenation, as solvent, optionally together with other solvents or diluents. In this case, a part of the product formed in the process can be mixed with the compound to be reacted, preferably hydrogenated. The weight of the hydrogenation product mixed as solvent or diluent is preferably 1 to 30 times the weight of the aromatic compound to be reacted, preferably hydrogenated,
It is more preferably 5 to 20 times, most preferably 5 to 10 times.

The above also applies to other compounds which are reacted according to the invention. Again, there are no restrictions on the solvent or diluent.

Examples of suitable solvents or diluents in the reaction of the polymer include the following: hydrocarbons such as hexane, cyclohexane, methylcyclohexane, heptane, octane, toluene, xylene and the like, and tetrahydrofuran, dioxane, dioxane. Butyl ether, methyl-t
linear or cyclic esters such as tert-butyl ether and the like, ketones such as methyl ethyl ketone and acetone, esters such as ethyl acetate, or DMF and N-
Amides such as methylpyrrolidone.

Preferably, cyclohexane, toluene or THF is used. Mixtures of these and other solvents and diluents can also be used.

If a polymer is obtained by solution polymerization, the resulting solution containing the polymer can also be reacted directly in the process according to the invention.

The amount of solvent or diluent used is not particularly limited within the process according to the invention and can be freely selected on demand. However, the polymer 1 to be reacted
Preference is given to an amount which results in a solution comprising 〜70%, preferably 1-40% by weight.

[0131] the reaction below will be described by hydrogenation reaction as an example, when carrying out the dehydrogenation or oxidation, gaseous hydrocarbons or oxygen-containing gas under the following conditions instead of hydrogen or a hydrogen-containing gas Can be used below.

The hydrogenation is carried out at a suitable pressure and temperature. Preferred is a pressure of about 2 × 10 ⁶ Pa or more, preferably 5 × 10 ⁶ Pa or more, and especially about 1 × 10 ⁷ to about 3 × 10 ⁷ Pa. Preferred temperatures are from about 30 to about 250 ° C, preferably from about 100 to 220 ° C, especially from about 150 to about 20 ° C.
0 ° C.

The hydrogenation can be carried out continuously or batchwise. If the process is carried out continuously, a portion of the hydrogenation product leaving the reactor can be added to the reactor feed upstream of the reactor. A portion of the hydrogenation product leaving the reactor is recycled as solvent so that the proportions mentioned under the heading "Solvents and diluents" are achieved. The remaining amount of hydrogenation products is recovered.

If the process is carried out continuously, the feed rate of the compound to be hydrogenated is preferably from about 0.05 to about 3 kg per liter of catalyst per hour, more preferably 1 hour per liter of catalyst.
About 0.1 to about 1 kg per liter.

The hydrogenation gas used may be any gas containing free hydrogen and having no harmful amounts of catalyst poisons such as CO. For example, reformer exhaust gas can be used. Pure hydrogen is preferably used as hydrogenation gas.

In the case of phenols and amines substituted by at least one optionally substituted C ₁ -C ₁₀ and / or alkoxy group, the resulting isomer ratio of cis- to trans-configuration products Can be changed over a wide range by changing reaction conditions (temperature, solvent).

If the aromatic compound in which at least one amino group is bound to an aromatic nucleus is to be hydrogenated using a catalyst as defined above, the hydrogenation may be carried out with ammonia or a dialkylamine such as methylamine, ethylamine, propyl It can also be carried out in the presence of an amine or dimethylamine, diethylamine or dipropylamine. A suitable amount of ammonia or mono- or dialkylamine is used, which is preferably from about 0.5 to about 50 parts by weight, more preferably from about 0.5 to about 50 parts by weight, in each case based on 100 parts by weight of the compound to be hydrogenated. Is about 1 to about 20 parts by weight. Particularly preferably, anhydrous ammonia or anhydrous amine is used.

For the oxidation, air or pure oxygen is generally used. Hydrocarbons, especially methane or natural gas, are used for dehydrogenation.

The invention is described in some more detail below with reference to examples, but examples 1-4 relate to the hydrogenation of aromatic compounds in which at least one hydroxyl group is attached to an aromatic nucleus. Relates to the hydrogenation of aromatic compounds in which at least one amino group is bound to an aromatic nucleus. Examples 8 to 12
Refers to the reaction of compounds having a C = O group, Examples 13-16
Refers to the reaction of the polymer.

[0140]

EXAMPLES Preparation of Catalyst 1 Aluminum oxide support in the form of a 4 mm extrudate containing mesopores and macropores and having a surface area (BET) of 238 m ² / g and a pore volume of 0.45 ml / g To
Ruthenium (III) nitrate having a concentration of 0.8% by weight
Impregnated with aqueous solution. 0.15 ml / g of pores in the carrier
(About 33% of the total pore volume) is 50 nm to 10000 nm
0.30 ml / g of pores in the support (about 67% of the total pore volume) had a diameter of 2 to 50 nm. The volume of solution absorbed by the support during the impregnation was approximately equal to the pore volume.

Next, the carrier impregnated with the ruthenium (III) nitrate solution was dried at 120 ° C.
Activated with The catalyst thus prepared contained 0.05% by weight of ruthenium, based on the weight of the catalyst.

[0142]Example 1  Concentration of p-tert-butylphenol in THF 50
A weight percent solution was prepared. Next, this solution 2500 g / h
With hydrogen at a temperature of 180 ° C. and 2.6 × 10⁷Pa
At a total pressure of 3.2 l of the Ru catalyst described above
Passed through the flow reactor. After removal of the solvent by distillation
In addition, the hydrogenated product had the following composition: -cis, trans-4-tert-butylcyclohexa
Nol 99.9% -p-tert-butylphenol <0.01%Example 2 Hydrogenation is carried out with p-tert-butylphenol in THF
3500 g of a 50% by weight solution of
Performed as described in Example 1, except that
did. After distillation of the solvent, the hydrogenation product has the following composition
Was: -cis, trans-4-tert-butylcyclohexa
Nol 99.8% -p-tert-butylphenol <0.01%Example 3 Hydrogenation is carried out with p-tert-butyl phthalate in isobutanol.
Example 1 except that a 50% by weight solution of phenol was used.
Performed as described in. Hydrogenation after distillation of solvent
The product had the following composition: -trans-4-tert-butylcyclohexanol
 67.5% -cis-4-tert-butylcyclohexanol 3
2.4% -p-tert-butylphenol <0.01%Example 4 In an autoclave with a volume of 3.5 l in THF
2 kg of a 50% by weight solution of bisphenol A in
500 ml of catalyst were placed in the catalyst basket. Then water
2 × 10 6⁷5 o'clock under pressure of Pa
Batched over time. The desired diol isomer
Conversion to cycloaliphatic mixture is quantitative, residual aromatization
The compound content was less than 0.01%.

Example 5 1.2 l of catalyst prepared as described above were charged to an electrically heated flow reactor. The hydrogenation of the aniline was then started at a temperature of 160 ° C. under a pressure of 2 × 10 ⁷ Pa without prior activation. The hydrogenation was carried out continuously in the ascending mode, a portion of the hydrogenation effluent was recycled via a circulation pump and added to the starting material upstream of the reactor. Thus, the amount of hydrogenated product added as solvent was ten times the amount of aniline. H at the top of the separator
_The pressure was reduced from 500 l / h to 600 l. The amount of aniline continuously fed to the corresponding reactor is at a space velocity of 0.6
kg / l · h.

As a function of reaction temperature, the following product composition was achieved under steady state reaction conditions:

[0145]

[Table 1]

[0146] Example 6 Hydrogenation, with continuous metered addition of anhydrous ammonia
Performed as described in Example 5, except where noted. Ani
Add 10 parts by weight of ammonia to 100% by weight of phosphorus.
I got it. Steady state of the following product composition as a function of reaction temperature
The reaction was achieved under the following reaction conditions:

[0147]

[Table 2]

Example 7 In an autoclave having a capacity of 3.5 l, 2 kg of a 50% by weight solution of toluylenediamine (2.4; a mixture of 2.6-diaminotoluene isomers) in THF and a catalyst as described above 500 ml were charged. The hydrogenation was then carried out batchwise for 5 hours at a temperature of 150 ° C. under a pressure of 2 × 10 ⁷ Pa. The conversion of the desired diamine to the cycloaliphatic mixture is quantitative, with a residual aromatics content of 0.1.
Less than 01%.

Example 8 13 l of catalyst were introduced into a tubular reactor (length = 2500 nm, diameter = 45 nm). Subsequently, n
Filled with butanol, 3 × 10 ⁶ Pa (30 bar)
Heated to 180 ° C. with hydrogen pressure. Then, an amount of 1 kg / h of n-butyraldehyde is continuously fed into the reactor in the amount of 50 kg.
It was introduced at a flow rate of 1 / h. The resulting reaction product was colorless and ruthenium-free.

According to gas chromatography measurement, 9
9.4% conversion and selectivity for n-butanol 9
9.7% (respectively relative to the amount of n-butyraldehyde introduced) was determined.

[0151]Example 9  13 l of catalyst, a copolymer of ethylene and CO (M_w5
000, CO content 35%) 700 g (THF 1300 g)
Was dissolved in a 3.5 l autoclave.

Subsequently, the mixture was hydrogenated at 180 ° C. and a hydrogen pressure of 2 × 10 ⁷ Pa (200 bar) for 5 hours.
The conversion to the desired polyalcohol was 93%, based on the amount of copolymer introduced.

Example 10 13 l of catalyst were introduced into a 3.5 l autoclave, into which 2000 g of benzaldehyde were introduced. Subsequently, the mixture is brought to 180 ° C. and a hydrogen pressure of 2 × 10 ⁷ Pa
(200 bar) for 10 hours. The conversion to the desired cyclohexylmethanol was 100% at a selectivity of 96.5% (each relative to the amount of benzaldehyde introduced).

Example 11 13 l of the catalyst were introduced into a 3.5 l autoclave, and 2,000 g of 2-ethylhexanol was introduced therein. Subsequently, the mixture is brought to 180 ° C. and a hydrogen pressure of 2 × 10 ⁷ Pa
(200 bar) for 10 hours. The conversion to the desired 2-ethylhexanol is 97.2% selectivity (each relative to the amount of 2-ethylhexanol introduced).
Was 100%.

Example 12 100 ml of adipodimethyl ester was reacted with catalyst 1 in a 0.3 l stirred autoclave. The mixture was stirred at a hydrogen pressure of 2 × 10 ⁷ Pa (200 bar) and a temperature of 220 ° C. for 12 hours. Gas chromatographic analysis of the product obtained shows a conversion of 98% for hexanediol and 91% with respect to the amount of adipodimethyl ester introduced.
% Yield was determined.

Preparation of Catalyst 2 An aluminum oxide support containing mesopores and macropores and having the form of a 4 mm extrudate having a surface area (BET) of 238 m ² / g and a pore volume of 0.45 ml / g was prepared. ,
Palladium (III) nitrate having a concentration of 0.8% by weight
Impregnated with aqueous solution. 0.15 ml / g of pores in the carrier
(About 33% of the total pore volume) is 50 nm to 10000 n
0.30 ml / g of pores in the carrier (about 67% of the total pore volume) had a diameter of 2-50 nm. The volume of solution absorbed by the support during the impregnation was approximately equal to the pore volume.

Next, the carrier impregnated with the palladium (III) nitrate solution was dried at 120 ° C. and activated (reduced) in a hydrogen stream at 200 ° C. The catalyst thus produced contained 0.05% by weight of palladium, based on the weight of the catalyst.

Example 13 Molecular weight of 300,000 (weight average) in cyclohexane
The catalyst described in 25 wt% solution 2kg and the three blocks of poly (styrene--co- butadiene -co- styrene) having a 1 (Ru0.5 wt% / Al ₂ O _3, the ratio of metal surface area to carrier surface area 0 0.001: 1) 500 ml
Was charged to an autoclave having a volume of 3.5 l.

The hydrogenation was then carried out batchwise under a pressure of 1 × 10 ⁷ Pa at 100 ° C. for 5 hours. The hydrogenated material content in the polymer was 95% and the aromatics content was the same as in the starting polymer. The molecular weight did not decrease.

Example 14 2 kg of a 50% by weight solution of polybutadiene having a molecular weight (weight average) of 6000 in cyclohexane and 1500 ml of the catalyst described above were charged to an autoclave having a capacity of 3.5 l. Next, the hydrogenation was
^It was carried out batchwise at 100 ° C. for 5 hours under a pressure of ⁷ Pa. The conversion of hydrogenated material in the polymer to the desired polymer was quantitative. The molecular weight did not decrease.

Example 15 2 kg of a 25% by weight solution of poly (acrylonitrile-co-butadiene) having a molecular weight (weight average) of 30,000 in tetrahydrofuran and catalyst 5 as described above
00 ml was charged to an autoclave having a capacity of 3.5 l. Next, hydrogenation was performed under a pressure of 1 × 10 ⁷ Pa for 1 hour.
The batch was run at 80 ° C. for 5 hours. The amount of hydrogenated material in the polymer was 92%. The nitrile content was 85% of the content in the starting polymer. The molecular weight did not decrease.

Example 16 Molecular weight of 300,000 in cyclohexane (weight average)
2 kg of a 25% by weight solution of triblock poly (styrene-co-butadiene-co-styrene) having the following formula: 500 m of catalyst 2 described above (Pd 0.5% / Al ₂ O ₃ )
l were charged to an autoclave having a capacity of 3.5 l.

The hydrogenation was then carried out batchwise under a pressure of 1 × 10 ⁷ Pa at 100 ° C. for 5 hours. The conversion to the desired partially saturated polymer was 97% and the aromatics content was 94% of the content in the starting polymer. The molecular weight did not decrease.

──────────────────────────────────────────────────続 き Continuation of front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C07C 29/20 9155-4H C07C 29/20 31/12 9155-4H 31/12 31/135 9155- 4H 31/135 31/20 9155-4H 31/20 Z 35/08 9155-4H 35/08 35/21 9155-4H 35/21 209/72 8828-4H 209/72 211/35 8828-4H 211/35 C08F 4/80 C08F 4/80 36/06 9062-4J 36/06 297/04 297/04 // C07B 61/00 300 C07B 61/00 300 (72) Inventor Konrad Knorr Ludwigshafen Germany Horst-Schölg-Strasse 184 (72) Inventor Sabine Weigny Germany Germany Weiterstadt Lindenstraße 36 (72) Inventor Jochem Henkelmann Germany Manha Im Basser Manstrasse 25 (72) Inventor Paul Negele Germany Otterstadt Zanderstrasse 43 (72) Inventor Hermann Gauzepol Germany Mutterstadt Me Darduslink 74 (72) Inventor Norbert Nisner Friedels Germany Heim Bourscher Hof 10 (72) Inventor Andreas Henne Neustadt-Ard-Korfink-Strasse 137 a.

Claims (3)

[Claims] 1. The catalyst according to claim 1, wherein ruthenium as active metal, alone or together with at least one Group Ib, VIIb or VIIIb metal, applied to the support, is based on the total weight of the catalyst.
In the method of reacting an organic compound in the presence of a catalyst containing 0.01 to 30% by weight, 10 to 50% of the pore volume of the carrier is composed of macropores having a pore size in the range of 50 nm to 10000 nm. A method of reacting an organic compound, wherein 50 to 90% of the pore volume of the carrier is composed of mesopores having a pore size in the range of 2 to 50 nm, and the sum of the pore volumes is 100%. 2. Ruthenium as active metal, alone or together with at least one Group Ib, VIIb or VIIIb metal, applied to the support, relative to the total weight of the catalyst,
Palladium as an active metal, alone or together with a Group Ib, VIIb or VIIIb metal, in the presence of a catalyst containing in an amount of 0.01 to 30% by weight or applied to a support,
In a process for the hydrogenation of polymers containing at least one C-C multiple bond in the presence of a catalyst containing in an amount of 0.01 to 30% by weight relative to the total weight of the catalyst, the catalysts defined above each 10 to 50% of the pore volume of the carrier is 50
consisting of macropores having a pore size in the range of 1 nm to 10000 nm, and 50 to 90% of the pore volume of the carrier is 2 to 2 nm.
A method for hydrogenating a polymer, comprising mesopores having a pore size in the range of 50 nm, wherein the sum of the pore volumes is 100%. 3. Ruthenium as active metal, alone or together with at least one Group Ib, VIIb or VIIIb metal, applied to the support, based on the total weight of the catalyst
Palladium as an active metal, alone or in an amount of 0.01 to 30% by weight, or applied to a carrier;
b, VIIb or VIIIb, together with a metal, in a quantity of 0.01 to 30% by weight, based on the total weight of the catalyst, the catalyst as defined above is each 10 to 50% of the pore volume of the support. % Consists of macropores having a pore size in the range of 50 nm to 10000 nm, and 50 to 90% of the pore volume of the carrier consists of mesopores having a pore size in the range of 2 to 50 nm. Is 100%.